CN113412835A - Synthesis method of novel chlamydomonas pheromone component - Google Patents
Synthesis method of novel chlamydomonas pheromone component Download PDFInfo
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- CN113412835A CN113412835A CN202110859628.7A CN202110859628A CN113412835A CN 113412835 A CN113412835 A CN 113412835A CN 202110859628 A CN202110859628 A CN 202110859628A CN 113412835 A CN113412835 A CN 113412835A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/298—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with manganese derivatives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a synthesis method of a novel clothianidin component, which takes terminal alkyne and alkyl bromide as initial raw materials and prepares the clothianidin component through coupling, reduction and oxidation reactions; the preparation method optimizes and improves the preparation route method, optimizes the specific reaction operation conditions, and ensures that the reaction stability is good, the repeatability is good, the reaction condition of the synthesis method is simple, and the cost is low; the operation danger level and the production cost are reduced; the operation safety is good, the post-treatment is green and environment-friendly, and the obtained chlamydomonas pheromone component has high purity; the method has the advantages of simple and easy steps, safe and cheap solvent and process conditions, environmental-friendly and green industrial production realization, and wide application prospect.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of a novel chlamydomonas moth pheromone component.
Background
The Chlamydomonas is belonging to the genus Chlamydomonas of the family Bombycidae of the order Lepidoptera, is widely distributed and is a global storage pest. The imago of the clotheshorse lays eggs on fur, feather, leather products and wood floor cracks, hair or dirty silk; the larvae will spin silk to make cocoons, and both ends are opened for food and movement. The larva grows in the cocoon, and still stays in the cocoon when pupating until the adult eclosion; the larvae of the clothiantus moth are small brown caterpillars, which are generally hidden in silk bags or nets (called drum nests), and on the wall a cement-bound spindle-shaped silk bag is visible, in which the larvae of a dark brown head are located. Wool, soft furniture, fur, carpet, blanket, fish meal, chemical fiber wool and cotton blended fabric stored in families can be eaten by larvae. In a library or a museum, larvae gnaw animal specimens and cause harm and damage to the animal specimens; adult clothespondoid is light yellow moth and is feared; the clothiantus armyworm does not eat, mating and laying eggs after eclosion into imagoes, and hatching the eggs into larvae for eating; therefore, cutting off mating at the adult stage of the chlamydomonas is a main mode for preventing and controlling the chlamydomonas; the clothiantus armyworm relies on pheromones to find mates for mating; therefore, in the prior art, the sex pheromone of the clothespondoid moth is used as bait to kill the clothespondoid moth so as to protect important museum collection animal specimens in a library or a museum.
The sex pheromone of the chlamydomonas mainly comprises: trans-2-octadecenal and trans-2, cis-13-octadecadienal; the structural formula is shown as the following formula: wherein formula A-a is trans-2-octadecenal, formula A-b is trans-2, cis-13-octadecadienal;
the sex pheromone preparation method of the clothiantus nudus disclosed in the prior art comprises the steps of taking cetyl alcohol as an initial raw material, oxidizing by PCC to obtain a hexadecanal intermediate compound, then coupling the hexadecanal intermediate compound with triethyl phosphonoacetate to obtain an ester with one increased carbon, and finally reducing the ester into alcohol and oxidizing by PCC to obtain a final product compound, wherein the route of the preparation method is shown in the following;
the sex pheromone preparation method of the chlamydomonas disclosed in the prior art has the advantages of low step reaction conversion rate, difficult purification of intermediate compounds and product compounds, low step reaction yield and low overall yield of the whole preparation method; reagents such as reduction and oxidation are frequently used in the operation conditions of each step, so that the operation safety is poor, the green and environment-friendly industrial production is not facilitated, and the industrial popularization and application are not facilitated.
Therefore, there is a need for developing and optimizing a preparation method of sex pheromone of the chlamydomonas, in particular a preparation method suitable for workshop amplification and realizing green environmental protection requirements.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the preparation method of the sex pheromone of the clothiantus armoricanus, which has the advantages of short flow, simple operation, low cost, environmental protection and suitability for industrial production.
The invention provides a synthesis method of a novel clothianidin component, wherein the clothianidin component comprises trans-2-octadecenal (the structure is shown as a formula A-a) and trans-2, cis-13-octadecadienal (the structure is shown as a formula A-b);
the preparation method comprises the following steps:
step 1, performing coupling reaction on a compound A-0 and a compound A-1 in a mixed solvent in the presence of a lithium reagent at a low temperature, and performing post-treatment to obtain a compound A-2;
step 2, carrying out a THP (protecting group) removal reaction on the compound A-2 in the presence of an acidic catalyst and an alcohol solvent, and carrying out post-treatment to obtain a compound A-3;
step 3, carrying out a step temperature control reaction on the compound A-3 in the presence of an oxygen-containing aprotic solvent and a reducing agent to carry out hydrogenation reaction, and carrying out post-treatment to obtain a compound A-4;
and 4, carrying out oxidation reaction on the compound A-4 in a mixed solvent in the presence of an oxidant, and carrying out post-treatment to obtain the compound (formula A) of the chlamydomonas moth pheromone component.
The preparation route is as follows:
wherein R is C12-C18 alkyl and C12-C18 alkenyl; x is halogen;
further, R is C14-C16 alkyl, C14-C16 alkenyl;
further, R is pentadecyl, cis 10-alkenylpentadecyl;
further, X is chlorine or bromine;
further, in the step 1, the mixed solvent is a mixed solvent of an oxygen-containing aprotic solvent and hexamethylphosphoric triamide;
further, in the mixed solvent, the volume ratio of the oxygen-containing aprotic solvent to the hexamethylphosphoric triamide is 1: 1-5: 1;
further, the oxygen-containing aprotic solvent is one or more of tetrahydrofuran, dimethyl tetrahydrofuran and dioxane;
further, in the step 1, the lithium reagent is one or more of n-butyl lithium, tert-butyl lithium, methyl lithium and phenyl lithium;
further, in the step 1, the molar ratio of the compound A-0 to the compound A-1 is 1: 0.9-1: 1.1;
further, in the step 1, the molar ratio of the compound A-0 to the lithium reagent is 1: 1-1: 1.5;
further, in the step 1, the weight-to-volume ratio (g/mL) of the compound A-0 to the mixed solvent is 1: 10-1: 20;
further, in the step 1, the low temperature is-50 to-78 ℃;
further, the step 1 specifically comprises: adding the compound A-0 and a lithium reagent into the mixture at the temperature of minus 78 ℃ by taking a mixed solvent as a solvent, and adding the compound A-1; reacting for 5-15 hours at room temperature, adding water to quench the reaction, and carrying out post-treatment to obtain a compound A-2;
wherein the content of the first and second substances,
the mol ratio of the compound A-0 to the compound A-1 to the lithium reagent is 1 (0.9-1.0) to 1.0-1.2; the weight-to-volume ratio (g/mL) of the compound A-0 to the mixed solvent is 1: 10-1: 14; in the mixed solvent, the volume ratio of the oxygen-containing aprotic solvent to the hexamethylphosphoric triamide is 2: 1-4: 1;
further, in the step 2, the acidic catalyst is p-toluenesulfonic acid, pyridine p-toluenesulfonate (PPTS);
further, in the step 2, the alcohol solvent is one of methanol, ethanol, tert-butyl alcohol and benzyl alcohol;
further, in the step 2, the molar ratio of the compound A-2 to the acidic catalyst is 1: 0.1-1: 0.3;
further, in the step 2, the weight-to-volume ratio (g/mL) of the compound A-2 to the alcohol solvent is 1: 3-1: 10;
further, the step 2 specifically includes: reacting the compound A-2 for 5-10 hours at room temperature in the presence of an acidic catalyst and an alcohol solvent, adding alkali to quench the reaction, and performing post-treatment to obtain a compound A-3;
wherein the molar ratio of the compound A-2 to the acidic catalyst is 1: 0.1-1: 0.2; the weight-to-volume ratio (g/mL) of the compound A-2 to the alcohol solvent is 1: 4-1: 5;
further, in the step 3, the oxygen-containing aprotic solvent is one or more of tetrahydrofuran, dimethyltetrahydrofuran and dioxane;
further, in the step 3, the reducing agent is lithium aluminum hydride or lithium aluminum hydride;
further, in the step 3, the molar ratio of the compound A-3 to the reducing agent is 1: 1.2-1: 2;
further, in the step 3, the weight-to-volume ratio (g/mL) of the compound A-3 to the oxygen-containing aprotic solvent is 1:3 to 1: 10;
further, the step 3 specifically includes: reacting the compound A-3 with a reducing agent in an inert gas environment by using an oxygen-containing aprotic solvent as a solvent at the temperature of-10-0 ℃ for 1-3 hours, then reacting at the temperature of 30-50 ℃ for 1-3 hours, adding water for quenching, and carrying out post-treatment to obtain a compound A-4;
wherein the molar ratio of the compound A-3 to the reducing agent is 1: 1.5-1: 2; the weight-to-volume ratio (g/mL) of the compound A-3 to the oxygen-containing aprotic solvent is 1:5 to 1: 9;
further, in the step 4, the oxidizing agent is electrolytic manganese dioxide;
further, in the step 4, the mixed solvent is a mixture of an alkane solvent and an oxygen-containing aprotic solvent;
further, the alkane solvent is heptane, hexane;
further, the oxygen-containing aprotic solvent is one or more of tetrahydrofuran, dimethyl tetrahydrofuran and dioxane;
further, in the mixed solvent, the volume ratio of the alkane solvent to the oxygen-containing aprotic solvent is 2: 1-5: 1;
further, in the step 4, the molar ratio of the compound A-4 to the oxidant is 1: 10-1: 30;
further, in the step 4, the weight-to-volume ratio (g/mL) of the compound A-4 to the mixed solvent is 1: 10-1: 20;
further, the step 4 specifically includes: reacting the compound A-4 for 1-3 hours at 0-20 ℃ in the presence of an oxidant and a mixed solvent of alkane and an oxygen-containing aprotic solvent, and carrying out post-treatment to obtain a chlamydomonas armyworm pheromone component compound (formula A);
wherein the molar ratio of the compound A-4 to the oxidant is 1: 20-1: 30; the weight-to-volume ratio (g/mL) of the compound A-4 to the mixed solvent is 1: 10-1: 15; in the mixed solvent, the volume ratio of the alkane solvent to the oxygen-containing aprotic solvent is 4: 1-5: 1.
According to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the mixed solvent is a mixed solvent of tetrahydrofuran and hexamethylphosphoric triamide;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the volume ratio of the mixed solvent of tetrahydrofuran and hexamethylphosphoric triamide in the mixed solvent is 2: 1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the volume ratio of the mixed solvent of tetrahydrofuran and hexamethylphosphoric triamide in the mixed solvent is 2.6: 1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the volume ratio of the mixed solvent of tetrahydrofuran and hexamethylphosphoric triamide in the mixed solvent is 4: 1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the weight-to-volume ratio (g/mL) of the compound A-0 to the mixed solvent is 1: 10;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the weight-to-volume ratio (g/mL) of the compound A-0 to the mixed solvent is 1: 12.5;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the weight-to-volume ratio (g/mL) of the compound A-0 to the mixed solvent is 1: 14;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the molar ratio of the compound A-0 to the compound A-1 is 1: 0.9;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the molar ratio of the compound A-0 to the compound A-1 is 1: 0.95;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the molar ratio of the compound A-0 to the compound A-1 is 1: 1.0;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the molar ratio of the compound A-0 to the lithium reagent is 1: 1.1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 1, the molar ratio of the compound A-0 to the lithium reagent is 1: 1.2;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 2, the molar ratio of the compound A-2 to the acidic catalyst is 1: 0.1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 2, the molar ratio of the compound A-2 to the acidic catalyst is 1: 0.15;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 2, the molar ratio of the compound A-2 to the acidic catalyst is 1: 0.2;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 2, the weight-to-volume ratio (g/mL) of the compound A-2 to the alcohol solvent is 1: 4;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 2, the weight-to-volume ratio (g/mL) of the compound A-2 to the alcohol solvent is 1: 4.8;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 2, the weight-to-volume ratio (g/mL) of the compound A-2 to the alcohol solvent is 1: 5;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 3, the molar ratio of the compound A-3 to the reducing agent is 1: 1.5;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 3, the molar ratio of the compound A-3 to the reducing agent is 1: 1.8;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 3, the molar ratio of the compound A-3 to the reducing agent is 1: 2;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 3, the weight-to-volume ratio (g/mL) of the compound A-3 to the oxygen-containing aprotic solvent is 1: 5;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 3, the weight-to-volume ratio (g/mL) of the compound A-3 to the oxygen-containing aprotic solvent is 1: 7;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 3, the weight-to-volume ratio (g/mL) of the compound A-3 to the oxygen-containing aprotic solvent is 1: 9;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the volume ratio of the alkane solvent to the oxygen-containing aprotic solvent in the mixed solvent is 4: 1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the volume ratio of the alkane solvent to the oxygen-containing aprotic solvent in the mixed solvent is 4.2: 1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the volume ratio of the alkane solvent to the oxygen-containing aprotic solvent in the mixed solvent is 5: 1;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the weight-to-volume ratio (g/mL) of the compound A-4 to the mixed solvent is 1: 10;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the weight-to-volume ratio (g/mL) of the compound A-4 to the mixed solvent is 1: 12;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the weight-to-volume ratio (g/mL) of the compound A-4 to the mixed solvent is 1: 15;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the molar ratio of the compound A-4 to the oxidant is 1: 20;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the molar ratio of the compound A-4 to the oxidant is 1: 25;
according to a preferred embodiment of the method for synthesizing the novel clothianidin component, in the step 4, the molar ratio of the compound A-4 to the oxidant is 1: 30.
The technical parameter characteristics in the above preparation method of the present invention can be combined at will.
In the above operations, the post-treatment includes, but is not limited to, stirring, liquid or solid transferring, water washing, alkali washing, acid washing, PH adjusting, filtering, ultrafiltration, circulating ultrafiltration, suction filtration, dilution, concentration, drying, recrystallization, freeze-drying, or the like, or one or more of stirring, liquid or solid transferring, water washing, alkali washing, acid washing, PH adjusting, filtering, ultrafiltration, circulating ultrafiltration, suction filtration, dilution, concentration, drying, recrystallization, freeze-drying, and the like.
In the field of chemical molecule synthesis, long-chain alkane and long-chain alkene belong to molecules with higher difficulty, the synthesis conversion rate is low, and the tracking and purification are difficult due to the molecular structure property. In the synthesis method, two compounds in the chlamydomonas moth pheromone component contain aldehyde groups on the basis of long chains, so that the stability of the compounds is reduced, and the aftertreatment and purification operations are more unfavorable.
Compared with the prior art, the synthesis method of the novel clothianidin component has the following beneficial effects:
according to the synthesis method of the novel clothianidin component, the synthesis reaction stability of the two components of the clothianidin is good, the repeatability is good, the reaction condition of the synthesis method is simple, and the cost is low by optimizing the synthesis route and the specific reaction operation condition;
according to the synthesis method of the novel chlamydomonas pheromone component, the single-step yield of each step of reaction is over 83 percent, and the yield is high; the purity of the compound of the chlamydomonas pheromone component product obtained by the synthesis method is improved to more than 95 percent, so that the production cost is effectively reduced; the intermediate in each step is easy to purify, and the post-treatment is simple, convenient and easy to operate
The synthesis method of the novel chlamydomonas moth pheromone component optimizes and improves the preparation route method, does not use expensive raw materials and dangerous raw materials, greatly reduces the preparation cost, has mild operation conditions, reduces the operation difficulty, has good safety, reduces the potential threat level of life hazard to staff in the production line, is green and environment-friendly in post-treatment, does not produce a large amount of corrosive sewage, reduces the safety level and the production cost of production, and is favorable for the application of green and environment-friendly industrial production;
in conclusion, the synthesis method of the novel chlamydomonas moth pheromone component optimizes and improves the preparation route method, optimizes the specific reaction operation conditions, and ensures that the reaction stability is good, the repeatability is good, the reaction conditions of the synthesis method are simple, and the cost is low; the operation danger level and the production cost are reduced; the operation safety is good, the post-treatment is green and environment-friendly, and the obtained chlamydomonas pheromone component has high purity; the method has the advantages of simple and easy steps, safe and cheap solvent and process conditions, environmental-friendly and green industrial production realization, and wide application prospect.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The synthesis method of the novel clothianidin component of the invention will be further described in detail in turn.
According to an exemplary embodiment of the present invention, the synthesis method of the clothianidin component comprises the following steps:
mixing the compound A-0 with an oxygen aprotic solvent, carrying out argon environment protection, cooling a reaction solution, adding a lithium reagent and a hexamethylphosphoric triamide solvent, and stirring for 1-3 hours to obtain a compound A-1; the molar ratio of the compound A-0 to the compound A-1 to the lithium reagent is 1:0.95: 1.1; the weight-to-volume ratio (g/mL) of the compound A-0 to the mixed solvent is 1: 12.5; in the mixed solvent, the volume ratio of the oxygen-containing aprotic solvent to the hexamethylphosphoric triamide is 2.6: 1; reacting the reaction solution at room temperature for 5-10 hours; sequentially adding water for treatment, concentrating, washing with water, extracting, drying, concentrating, and purifying by column chromatography to obtain compound A-2;
mixing the compound A-2, an acid catalyst and an alcohol solvent, wherein the molar ratio of the compound A-2 to the acid catalyst is 1: 0.15; the weight-to-volume ratio (g/mL) of the compound A-2 to the alcohol solvent is 1: 4.8; reacting for 5-10 hours at room temperature; sequentially adding an alkali solution, concentrating, washing with water, extracting, drying, concentrating, and purifying by column chromatography to obtain a compound A-3;
in an inert gas environment, mixing a reducing agent and an oxygen-containing aprotic solvent, feeding, cooling to-10-0 ℃, and adding a compound A-3; the molar ratio of the compound A-3 to the reducing agent is 1: 1.8; the weight-to-volume ratio (g/mL) of the compound A-3 to the aprotic solvent is 1: 7; reacting for 1-3 hours at the temperature of-10-0 ℃, and then reacting for 1-3 hours at the temperature of 30-50 ℃; sequentially adding water for treatment, concentrating, and purifying by column chromatography to obtain compound A-4;
mixing an oxidant and an alkane solvent, feeding, cooling to 0 ℃, and adding a compound A-4 and an oxygen-containing aprotic solvent; the molar ratio of the compound A-4 to the oxidant is 1: 25; the weight-to-volume ratio (g/mL) of the compound A-4 to the mixed solvent is 1: 12; in the mixed solvent, the volume ratio of the alkane solvent to the oxygen-containing aprotic solvent is 4.2: 1; heating the reaction solution to 10-30 ℃ for reaction for 2-4 hours; sequentially carrying out suction filtration, concentration and column chromatography purification to obtain the chlamydomonas pheromone component compound (formula A).
The purity of the compound (formula a) of the chlamydomonas pheromone component prepared by the preparation method of the embodiment is 95% or more.
The following examples will further illustrate the compounds of the pheromone component (formula A) of the present invention.
R is pentadecyl and X is bromine, to prepare the compound of formula A-a
Examples 1,
1) Adding 1.1 g of the compound A-0 into a dry 100ml four-neck flask, adding 10ml of anhydrous THF, cooling to-78 ℃ under the protection of argon, and adding 4.5ml of n-butyllithium and 3.8ml of hexamethylphosphoric triamide; stirring for 0.5h at-78 ℃ after the dropwise addition is finished; then adding a tetrahydrofuran solution of 1-bromopentadecane; reacting for 8 hours at the room temperature of the reaction solution; after quenching by adding water, concentrating, washing with water and extracting to obtain a crude compound, and purifying by column chromatography to obtain a compound A-2a (2.16 g, yield 83%);
2) adding 1.73 g of the compound A-2a into 8.3ml of a methanol solution, and then adding 0.16 g of p-toluenesulfonic acid; reacting for 8 hours at room temperature; adding sodium carbonate to adjust the system to be alkaline, then concentrating until the system is washed and extracted by dry water to obtain a crude product, and purifying by column chromatography to obtain a compound A-3a (1.39 g, yield 90%);
3) introducing argon into a dried 25ml three-neck flask, and adding 0.21 g of lithium aluminum hydride and 5ml of anhydrous THF; the temperature was reduced to-10 ℃ and 1.12 g of compound A-3a (diluted with 3ml of anhydrous THF) were added; reacting for 2 hours at the temperature of minus 10-0 ℃, and then reacting for 2 hours at the temperature of 30-50 ℃; quenching with water, filtering, concentrating to dryness to obtain crude product, and purifying by column chromatography to obtain compound A-4a (0.93 g, yield 83%);
4) to a dried 25ml three-necked flask, 5.83 g of electrolytic manganese dioxide, 8.5ml of heptane were added; after cooling to 0 ℃ 0.83 g of compound A-4a are added and diluted with 2ml of anhydrous THF); heating the reaction solution to room temperature for reaction for 2 hours; the reaction solution was filtered, concentrated to dryness to give a crude product, which was purified by column chromatography to give the product compound A-a (0.73 g, 88% yield, white solid).
Examples 2,
1) Adding 1.2 g of the compound A-0 into a dry 100ml four-neck flask, adding 10ml of anhydrous THF, cooling to-78 ℃ under the protection of argon, and adding 4.8ml of n-butyllithium and 2.5ml of hexamethylphosphoric triamide; stirring for 0.5h at-78 ℃ after the dropwise addition is finished; then adding a tetrahydrofuran solution of 1-bromopentadecane; reacting the reaction solution for 5 hours at room temperature; after quenching by adding water, concentrating, washing and extracting to obtain a crude compound, and purifying by column chromatography to obtain a compound A-2a (2.22 g, yield 84%);
2) adding 1.9 g of the compound A-2a into 7.6ml of a methanol solution, and then adding 0.17 g of p-toluenesulfonic acid; reacting for 10 hours at room temperature; adding sodium carbonate to adjust the system to be alkaline, then concentrating until the system is washed and extracted by dry water to obtain a crude product, and purifying by column chromatography to obtain a compound A-3a (1.6 g, yield 89%);
3) introducing argon into a dried 25ml three-neck flask, and adding 0.21 g of lithium aluminum hydride and 5ml of anhydrous THF; the temperature is reduced to-10 ℃ and 1.21 g of compound A-3a (diluted with 1ml of anhydrous THF) are added; reacting for 2 hours at the temperature of minus 10-0 ℃, and then reacting for 2 hours at the temperature of 30-50 ℃; quenching with water, filtering, concentrating to dryness to obtain crude product, and purifying by column chromatography to obtain compound A-4a (1.1 g, yield 92%);
4) to a dried 25ml three-necked flask was added 4.63 g of electrolytic manganese dioxide, 6ml of heptane; after cooling to 0 ℃ 0.73 g of compound A-4a are added and diluted with 1.5ml of anhydrous THF); heating the reaction solution to room temperature for reaction for 3 hours; the reaction solution was filtered, concentrated to dryness to give a crude product, which was purified by column chromatography to give the product compound A-a (0.66 g, 89% yield, white solid).
R is cis-10-alkenylpentadecyl and X is bromine, to prepare formula A-b;
examples 3,
1) Adding 1.65 g of the compound A-0 into a dry 100ml four-neck flask, adding 14ml of anhydrous THF, reducing the temperature to-78 ℃ under the protection of argon, and dropwise adding 6.8ml of n-butyl lithium and 5.7ml of hexamethyl phosphoric triamide; after the dropwise addition is finished, reacting for 1h at-78 ℃; then dripping tetrahydrofuran solution of cis 10-pentadecabromoolefin; reacting for 10 hours at the room temperature of the reaction solution; adding water for quenching, concentrating, washing with water, extracting to obtain a crude product, and purifying by column chromatography to obtain a compound A-2b (3.16 g, yield 82%);
2) adding 2.6 g of the compound A-2b into 12.3ml of a methanol solution, and then adding 0.24 g of p-toluenesulfonic acid; reacting for 5 hours at room temperature; adding sodium carbonate to adjust the system to be alkaline, then concentrating until the system is washed and extracted by dry water to obtain a crude product, and purifying by column chromatography to obtain a compound A-3b (2.1 g, the yield is 91%);
3) introducing argon into a dried 25ml three-neck flask, and adding 0.315 g of lithium aluminum hydride and 8ml of anhydrous THF; after cooling to-10 ℃ 1.68 g of compound A-3b (diluted with 3ml of anhydrous THF) was added; reacting for 2 hours at the temperature of minus 10-0 ℃, and then reacting for 2 hours at the temperature of 30-50 ℃; quenching with water, filtering, concentrating to dryness to obtain crude product, and purifying by column chromatography to obtain compound A-4b (1.41 g, yield 85%);
4) to a dried 25ml three-necked flask was added 8.75 g of electrolytic manganese dioxide, 12.5ml of heptane; after cooling to 0 ℃ 1.25 g of compound A-4b (diluted with 3ml of anhydrous THF) were added; heating the reaction solution to 10 ℃ and reacting for 1 h; the reaction solution was filtered, concentrated to dryness to give a crude product, which was purified by column chromatography to give the product compound A-b (1.05 g, 85% yield, colorless oily liquid).
Examples 4,
1) Adding 1.5 g of the compound A-0 into a dry 100ml four-neck bottle, adding 14ml of anhydrous THF, reducing the temperature to-78 ℃ under the protection of argon, and dropwise adding 6.0ml of n-butyl lithium and 7ml of hexamethyl phosphoric triamide; after the dropwise addition is finished, reacting for 1h at-78 ℃; then dripping tetrahydrofuran solution of cis 10-pentadecabromoolefin; reacting for 10 hours at the room temperature of the reaction solution; adding water for quenching, concentrating, washing with water, extracting to obtain a crude product, and purifying by column chromatography to obtain a compound A-2b (3.06 g, yield 88%);
2) adding 2.6 g of the compound A-2b into 13ml of methanol solution, and then adding 0.32 g of p-toluenesulfonic acid; reacting for 5 hours at room temperature; sodium carbonate is added to adjust the system to be alkaline, and then the mixture is concentrated to be dry, washed and extracted to obtain a crude product which is purified by column chromatography to obtain a compound A-3b (2.2 g, the yield is 93%);
3) introducing argon into a dried 25ml three-necked flask, and adding 0.315 g of lithium aluminum hydride and 10.5ml of anhydrous THF; after cooling to-10 ℃ 1.5 g of compound A-3b (diluted with 3ml of anhydrous THF) was added; reacting at the temperature of minus 10-0 ℃ for 1 hour, and then reacting at the temperature of 30-50 ℃ for 1 hour; quenching with water, filtering, concentrating to dryness to obtain crude product, and purifying by column chromatography to obtain compound A-4b (1.3 g, yield 86%);
4) to a dried 25ml three-necked flask was added 9.5 g of electrolytic manganese dioxide, 13.7ml of heptane; after cooling to 0 ℃ 1.1 g of compound A-4b (diluted with 2.7ml of anhydrous THF) was added; heating the reaction solution to 10 ℃ and reacting for 1 h; the reaction solution was filtered, concentrated to dryness to give a crude product, which was purified by column chromatography to give the product compound A-b (0.98 g, 88% yield, colorless oily liquid).
In the case of other similar implementations of the invention,
in the steps 1, 3 and 4, tetrahydrofuran can be replaced by dioxane and dimethyl furan;
in the step 2, the methanol can be replaced by ethanol, tert-butyl alcohol and benzyl alcohol;
in the above step 4, heptane may be replaced with hexane.
Test example 5:
the components of the prepared clothianidin of the above embodiment: and (3) carrying out stability determination on trans-2-octadecenal (the structure is shown as a formula A-a) and trans-2, cis-13-octadecadienal (the structure is shown as a formula A-b), sealing and placing the sample at normal temperature for six months, sampling, observing the appearance and detecting the purity, wherein the purity of the compound A is more than 95%.
Compared with the sample before placement, the compound A-a and A-b samples have no obvious change in appearance after 6 months of placement, and have no obvious reduction in purity. The fact that the compound A of the chlamydomonas pheromone component prepared by the preparation method has good stability and is beneficial to storage and transportation is shown.
The above examples and experimental examples show that the purity of the components of the chlamydomonas moth pheromone prepared by the preparation method is more than 95%, and the product stability is good. The method has the advantages of simple and convenient operation of each step, easy purification, simple and convenient post-treatment, environmental protection, easy operation, safe and feasible solvent and conditions, contribution to environmental protection, industrial amplification production and wide application prospect.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (9)
1. A method for synthesizing a novel chlamydomonas component is characterized in that the chlamydomonas component comprises trans-2-octadecenal (the structure is shown as A-a), and trans-2, cis-13-octadecadienal (the structure is shown as A-b);
the preparation method comprises the following steps:
step 1, performing coupling reaction on a compound A-0 and a compound A-1 in a mixed solvent in the presence of a lithium reagent at a low temperature, and performing post-treatment to obtain a compound A-2;
step 2, carrying out a THP (protecting group) removal reaction on the compound A-2 in the presence of an acidic catalyst and an alcohol solvent, and carrying out post-treatment to obtain a compound A-3;
step 3, carrying out a step temperature control reaction on the compound A-3 in the presence of an oxygen-containing aprotic solvent and a reducing agent to carry out hydrogenation reaction, and carrying out post-treatment to obtain a compound A-4;
and 4, carrying out oxidation reaction on the compound A-4 in a mixed solvent in the presence of an oxidant, and carrying out post-treatment to obtain the compound (formula A) of the chlamydomonas moth pheromone component.
The preparation route is as follows:
wherein R is C12-C18 alkyl and C12-C18 alkenyl; x is halogen.
2. The method of claim 1,
r is C14-C16 alkyl and C14-C16 alkenyl.
3. The method according to claim 1, wherein, in the step 1,
the mixed solvent is a mixed solvent of an oxygen-containing aprotic solvent and hexamethylphosphoric triamide;
in the mixed solvent, the volume ratio of the oxygen-containing aprotic solvent to the hexamethylphosphoric triamide is 1: 1-5: 1;
the lithium reagent is one or more of n-butyl lithium, tert-butyl lithium, methyl lithium and phenyl lithium.
4. The method according to claim 1, wherein, in the step 1,
the molar ratio of the compound A-0 to the compound A-1 is 1: 0.9-1: 1.1;
the molar ratio of the compound A-0 to the lithium reagent is 1: 1-1: 1.5;
the weight-volume ratio of the compound A-0 to the mixed solvent is 1: 10-1: 20.
5. The method according to claim 1, wherein, in the step 2,
the acid catalyst is p-toluenesulfonic acid;
the alcohol solvent is one of methanol, ethanol, tert-butyl alcohol and benzyl alcohol;
the molar ratio of the compound A-2 to the acidic catalyst is 1: 0.1-1: 0.3;
the weight-volume ratio of the compound A-2 to the alcohol solvent is 1: 3-1: 10.
6. The method according to claim 1, wherein, in the step 3,
the oxygen-containing aprotic solvent is one or more of tetrahydrofuran, dimethyl tetrahydrofuran and dioxane;
the reducing agent is lithium aluminum hydride or lithium aluminum hydride;
the molar ratio of the compound A-3 to the reducing agent is 1: 1.2-1: 2;
the weight-volume ratio of the compound A-3 to the oxygen-containing aprotic solvent is 1: 3-1: 10.
7. The method according to claim 1, wherein, in the step 4,
the oxidant is electrolytic manganese dioxide;
the mixed solvent is a mixture of an alkane solvent and an oxygen-containing aprotic solvent;
in the mixed solvent, the volume ratio of the alkane solvent to the oxygen-containing aprotic solvent is 2: 1-5: 1.
8. The method according to claim 1, wherein, in the step 4,
the molar ratio of the compound A-4 to the oxidant is 1: 10-1: 30;
the weight-volume ratio of the compound A-4 to the mixed solvent is 1: 10-1: 20.
9. A Chlamydomonas moth pheromone component prepared by the method of any one of claims 1 to 8, wherein the purity of the Chlamydomonas moth pheromone component is above 95%.
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